Oxydehydrogenation process

ABSTRACT

Conjugated dienes, such as butadiene, are prepared from monoolefins, such as butene-1, by oxydehydrogenation over a catalyst represented by the following general formula:

United States Patent [191 Takenaka et a1.

[ OXYDEHYDROGENATION PROCESS [75] inventors: Shigeo Takenaka; Akira lwamoto,

both of Takasaki, Japan [73] Assigneez Nippon Kayaku Kabushiki Kaisha,

Tokyo, Japan 22 Filed: on. 20, 1970 21 Appl. No.: 82,489

[30] Foreign Application Priority Data Feb. 5, 1970 Japan i. 45/9603 [52] [1.8. CI. 260/680 E, 252/432, 252/437 [51] Int. Cl. C07c 5/18 [58] Field of Search 260/680 E [56] References Cited UNITED STATES PATENTS 3,414,631 12/1968 Grasselli et a1. 260/680 3,453,344

7/1969 Aliev et a1. 260/680 Oct. 9, 1973 3,522,299 7/1970 Takenaka et al. 260/604 X 3,576,764 4/1971 Yamaguchi et a1... 252/437 3,642,930 2/1972 Grasselli et al. 260/680 Primary Examiner--Paul M. Coughlan, Jr. Attorney-Russell & Nields [57] ABSTRACT Conjugated dienes, such as butadiene, are prepared from monoolefins, such as butene-l, by oxydehydrogenation over a catalyst represented by the following general formula:

5 Claims, No Drawings Single pass yield pass yield of butadiene and isoprene of up to 96 per- OXYDEl-IYDROGENATION PROCESS DESCRIPTION AND BACKGROUND OF THE INVENTION Nl Co Fe L Mn MO; 0,,

in which L is phosphorus, arsenic or boron, M is potassium, rubidium or cesium; and wherein a and b have a value of from to 15, a-l-b being 2 to 15, c is 0.5 to 7, d is 0.1 to 4, e is 0.1 to 4,fis 12, g is number determined by the valence requirements represented by Ni, Co, Fe, Bi, L, M and Mo, and his 0.01 to 1.0.

In this specification, the terms conversion, selectivity and single pass yield are defined as follows:

mols of monoolefin reacted Convers1on(%)= mols of monoolefin supplied mols of conjugated diene formed mols of monoolefin reacted Selectivity (7c) mols of conjugated diene formed mols of monoolefin supplied Previous attempts to produce dienes by catalytic oxydehydrogenation of monoolefins, similar to the-present invention, are disclosed in US. Pat. No. 3,414,631. In this patent, monoolefins are converted to dienes by the use of a catalyst represented by the formula A, B, Fe, Bi P, Mo, 0, wherein A is nickel or a combination of nickel and cobalt, B is at least one member selected from the group consisting of antimony, tin, copper and arsenic, and the maximum single pass yield of butadiene and isoprene is 83.1 percent and 31.8 percent, respectively.

The present invention has been accomplished as a result of various studies to further raise the single pass yield of conjugated dienes. The present catalyst is distinctive, among other reasons, because it contains potassium, rubidium or cesium.

In the present invention, the catalyst comprising Co, Fe, Bi, P, K, Mo and O is most preferable, and a single cent and 71 percent, respectively, is achieved by the catalyst. Butadiene was produced from a n-butene, and isoprene was produced from 2-methyl-butene-2, 2- methyl-butene-l and 3-methyl-butene-l. In accordance with the invention oxidation to maleic acid, carbon monoxide, carbon dioxide etc. is inhibited.

The present catalyst may be prepared by any suitable method of combining the various metals or metal oxides, preferably with a binder or on a carrier. A suitable procedure is to form a slurry or solution of compound in proper proportions, for example, by adding to an aqueous molybdate solution, such as ammonium molybdate, an L compound, such as phosphoric, arsenic or boric acid and an M compound, such as potassium, rubidium or cesium nitrate, and then by adding watersoluble compounds of nickeLcobalt, iron and bismuth as the occasion demands.

A suitable carrier may then be added to the slurrylike suspension, which is then heated to dryness to form a cake. The cake may be pelleted and calcined to provide the final catalyst.

In place of ammonium molybdenum oxide or molybdic acid may be used to provide Mo. Potassium molybdate may be used to provide both Mo and M. The remaining metals, nickel, cobalt, iron and be provided as nitrates.

The catalyst of the invention is preferably incorporated on a carrier material, such as silica, silicon carbide or alumina. Silica gel or silica sol is particularly suitable. The catalyst is preferably in the form of grain or tablet. Generally, the catalyst is employed as a fixed bed, but it may be a moving bed or fluidized bed, as well.

The catalytic oxydehydrogenat-ion reaction of the invention is carried out by the oxydehydrogenation of olefins to diene, preferably at a temperature of about 250500C and at pressure of 0.5-10 atm. The contact time of monoolefin, air and steam preferably is about 0.5-8 seconds, under normal pressure and reaction temperature. The gaseous mixture to be passed over the catalyst is preferably prepared by mixing a monoolefin, air and steam so as to give a proportion of.

0.25- 3 mols of oxygen and 1-20 mols of water to 1 mol of monoolefin. Thefollowing examples are given in order to illustrate the invention without limiting the same.

EXAMPLES 1-5 22.0g of nickel nitrate, 39.4g of cobalt nitrate and 36.6g of ferric nitrate was dissolved in distilled water, respectively, and-14.7g of bismuth nitrate was dissolved in distilled water acidified with concentrated nitric acid and those nitrate solutions were mixed.

Sufficient phosphoric acid (85 percent) and potassium nitrate, respectively, to provide a final product having a value of e of 0.5 and of h of 0.03, was added to an aqueous solution of 63.6g of ammonium molybdate dissolved in distilled water and then the foregoing mixed nitrate solution was added.

10g of silica sol (as Si 0 was added, and the resulting suspension heated to dryness, and further calcined bismuth, may

121025, was passed over the catalyst, for a Contact time of 2.5 seconds, while the niter bath temperature was 305C.

For examples 2-5 the procedure of example 1 was solution, and combined with 63.6g of ammonium molybdate dissolved in distilled water; with heating and stirring. 18.1g of silica sol (as Si was added to the resulting solution and then 22.0g of nickel nitrate,

The by-products principally were minor amounts of carbon monoxide, carbon dioxide, maleic acid, acrylic acid and acetic acid.

EXAMPLES 6-17 EXAMPLE 18 Except for the use of butene-2, consisting of transbutene-2 (80 percent) and cis-butene-2 percent), in the place of butene-l, and bath temperature 350C, the catalyst and reaction conditions were the same as in Example 2. The results were: conversion of 95 percent, selectivity of 90 percent, and single pass yield of percent.

EXAMPLE l9 1.69g of phosphoric acid (85 percent) and 0.219g of potassium nitrate was added and dissolved in aqueous followed, with variations in the phosphorous (e) or po- 5 39.4g of cobalt nitrate and 36.6g of ferric nitrate, retassium (h) constituents and bath temperature as spectively, dissolved in distilled water and 14.7g of bisshown in table I. muth nitrate dissolved in distilled water acidified with The products of examples l-5 were analyzed by gasconcentrated nitric acid were added. liquid chromotographic analysis (G.L.C.), and the acid The suspension produced was stirred and dried over by-product was determined by values of conversion, 10 a water bath. The dried cake was calcined for 4 hours selectivity and yield shown in table I. at 650C in air and pulverized to about 20 mesh.

TABLE I Single pass Nitcr b h Conversion Selectivity yield of Example 7 Value Value Temperature ofbutene-l ofbutadiene V lgutadiene gf f} (0) a TABLE 11 Selectiv- Single in. mm. Bath sion of ity of pass yield Example temp. butene-l butadiene of buta- No. V Composition of the catalyst l" C) diene 6 Ni2,5C04 .-,Fe Bi1ASu 5Ku. mM0|2O54 320 98 97 7 2.5 4.s a i u.s o.:m i2Os4 320 98 97 95 8 Ni Co ,5Fe Bi Pn 5Rbo miM0 2O54 320 89 89 9 Ni Co Fe Bi P Cs Mo, O 320 95 93 88 10 cOgFfi Bl po KmmtMo gom l l Ni Fe BhP K Mo O 1 93 12 Nl1COzF3Bl3P1Ko,1MO O 320 97 95 92 13 lU QJI Ofi UASK0.0BM012O54 340 97 91 88 14 Ni Co FeaBi Pn K0 0aM0 O51 300 96 9O 86 15 l4 06FEi.sBln.s n.s n.0a i2 55 320 95 95 i 90 16 Ni2,5CO ,5Fe Bi PiK Mo O 365 93 93 86 17 M OMFBaB t u.:sKu.n5 |2 s4 310 97 95 92 The catalyst composition was 60 ml of the catalyst was used in a stainless steel reactor having an inner diameter of 20 mm. The reactor was immersed in a niter bath, and a reactant stream of 2-methyl-3-butene air and steam in a mole ratio of 1:10:10 was passed over the catalyst, with a contact time (based on reaction temperature) of about 3.5 sec.

The niter bath temperature and the results of reaction are shown in the Table III.

The by-products included isomerized 2-methyl-3- butene, 2-methyl-l-butene and Z-methyl-Z-butene, carbon monoxide, carbon dioxide and others, for example. aldehydes and organic acids.

TABLE 111 Con- Single Niter bath version Selectivity pass yield of isoprene of isoprene 0 Temp. (C) 336 56.8 8L0 45.9 343 74.0 83.3 61.7

EXAMPLE 19a In order to provide a comparative example, potassium nitrate was omitted from the catalyst preparation of Example 19, and the resulting catalyst composition was represented by formula 2.s 4.s 3.o 1.o ms n u- The reaction condition was the same as that of Example 19 except the bath temperature was raised to 358C. for raising of the single pass yield of isoprene.

The results were: conversion, 82.3 percent, selectivity, 32.6 percent, and single pass yield, 26.8 percent.

EXAMPLES 20-34 amples 29 and 32, cobalt nitrate was omitted in Exam- 1 ple 30, phosphoric acid was omitted in Example 20, arsenous acid in Example 25 and boric acid in Example 26 were substituted for phosphoric acid, and rubidium nitrate in Example 27 and cesium nitrate in Example 28 were substituted for potassium nitrate. In each Example the proportions of the various ingredients were chosen to yield ultimate catalysts having the formulas in Table IV.

EXAMPLE 35.

The catalyst of Example 22 was used to convert a reactant stream of 2-methyl-1-butene, air and water (steam) in the molar ratio of 1:16:16, respectively. The bath temperature was 330C. The results are shown in Table V. Otherwise, the reaction conditions were the same as for Example 19.

EXAMPLE 36 The catalyst of Example 22 was again used to convert a feed streamv of 2-methyl-2-butene, air and water (steam) in the molar ratio of 1:20:21, respectively, and the bath temperature was 320C. Otherwise, Example 19 was followed. The results are shown in Table V.

'19 were produced by the same procedureexcept that the catalysts were calcined for 4 hours at 500, 550, 600 and 700C, respectively. The reaction conditions were the same as described in Example 19, aside from bath temperature. The results were shown in Table VI.

EXAMPLE 38 The same catalyst as that of Example 29 was used. The reaction conditions were the same as that of Example 19 except that the feed was composed of 2-methyl- 3-butene, air and steam in mol ratio of 1:5.0:9.3, respectively, and the bath temperature was raised to 357C.

The results were: conversion, 77 percent, selectivity,

92 percent, and single pass yield, 71 percent.

EXAMPLE 39 A catalyst having the composition presented by the formula 10 lLS as 05 ama 12 54 i was obtained by a procedure similar to that described in Examples l-5, and was used to produce butadiene from butene-l by oxydehydrogenation.

The feed stream was butene-l, air and steam, in a mole ratio of 1:l0:5; contact time was 2.5 seconds, and the njter bath temperature was 340C.

The results were: conversion, 96 percent, selectivity,

93 percent, and single pass yield, 89 percent.

EXAMPLES 40-41 Catalysts having the composition presented by the formulas.

mo m 1.0 0.5 0.10 12 50 and 60 r. no 05 040 12 &0

were produced by the procedure similar tothat de- 45 scribed in Examples '19-34.

TAB LE lV Conversion Single pass B h of Z-methyl- Selectivity yield of Example temp. 3-butene of isoprene isoprene o. Composition ofthe catalyst 2 2,5C0t.5F. .0Bl|,uK0.lm lz szi 340 72 78 56 21 iTa LS 10 Ll1 2JJ JLHHMOI ZOEm 348 67 82 22 N1 C0 5Fe:x uBii.nPn sK4Lm MO gO 337 73 88 64 2 N s ut :;.n i.uPn 5KrL-nmMOrgOm 351 66 86 57 24 N 'v -LS ILID LU ALSKLZUJ IZ M 351 75 87 25 N sCQmF:i,n li.uA5o,s o.ine ie m 335 70 59 2 N a taF muBi .nBtmKunueM le st 4 71 84 59 27 N -,C0,;,F.1,"Bi| P" Rbu,mM0,- -O 330 72 87 63 28 N LA LI- :t,nB Lo lm u.mz iie st 330 74 85 63 29 061i el,lI l.U llj flJlH HOMl 5 75 i 68 30 lLuFBm 11.uPo.:.Kn.mz |2 s1 3 I5 74 73 54 Si Ni uCumuFfiLnBi;\.u Kn,luzMOuOng 7] 70 50 HLuFEILA 10.5PrmKlLmziW tz sl 350 76 88 7 33 N |.UCQ uFCupBi u u Ku,mg MO g 34 zu'v k Lr-F zt li lKnJMOu m. 67 ()4 43 EXAMPLES 37a-d Four catalysts having the same composition (Ni Co Fe Bi P K Mo 0 as that of Example 5 The catalysts were used to produce isoprene from 2- methyl-3-butene by oxydehydrogenation, by a procedure similar to that of Example 19. The bath temperature and the results of reaction are shown in Table Vll.

TABLE ll H Niter 1W, .M.. s s-.... hath Convey Selectivity ingle ass P s. lqm I sigg ofisoprene v yiedof No. lsopentene as materiai (75) (76) isoprene(%) 3s Z-rnethyl-l-butene '330 97 59 57 36 Z-methyl-Z-butene 320 90 65 59 10 r TABLE VI Nl 'co Fe B1,, L, M, Mo, 0,,

Selectivity 31,121 Example Calcined hliterbath qm l fj pfisDprenF V aggi; I 3 W T W ,H.. A s I No. temp. l Te psio isoprene 95 wherein L is phosphorus, arsenic or boron and M is po- 373 500 314 7&7 57.6 441 I5 tassium, rubidium or cesium, and wherein a and b have 3gb 23g 2g; a value of from 0-15, a+b being 2 to 15, c 0.5 to 7, 2 700 340 1 1 d is 0.1 to 4, e is 0 to 4, f is 12, g is a number determined by the valence requirements represented by Ni, Co, Fe, v Wm Bi, L, M and Mo, and h is 0.01 to 1.0, under reaction conditions sufficient to convert said butene to butadi- TABLE v11 2. The process of claim 1, wherein said catalyst is in- Maw M,, hsinglqg ss corporated on a silica carrier. .7 xamp rNitq s a h C m e selectiyily 2Q. yi l fli 3. The process of claim 1, wherein the reaction is car- NO- temp. C) sion isoprene isoprene -ried out in the presence of steam. 41 350 76 88 67 4. The process of claim 1, wherein the reaction is car- 42 t 345 73 89 65 ried out at a temperature of from 250 to 500C.

my 5. The process of claim 1, wherein said feed stream We claim: comprises steam and has a molar ratio of oxygen, steam 1. A catalytic oxydehydrogenation process, which comprises passing a feed stream comprising butene and molecular oxygen over a catalyst having the composition:

and monoolefin of 0.253:1-20:1. 

2. The process of claim 1, wherein said catalyst is incorporated on a silica carrier.
 3. The process of claim 1, wherein the reaction is carried out in the presence of steam.
 4. The process of claim 1, wherein the reaction is carried out at a temperature of from 250* to 500*C.
 5. The process of claim 1, wherein said feed stream comprises steam and has a molar ratio of oxygen, steam and monoolefin of 0.25-3:1-20:1. 